CN108504136B - A kind of blue anthraquinone reactive disperse dyes and preparation method thereof - Google Patents

A kind of blue anthraquinone reactive disperse dyes and preparation method thereof Download PDF

Info

Publication number
CN108504136B
CN108504136B CN201810515538.4A CN201810515538A CN108504136B CN 108504136 B CN108504136 B CN 108504136B CN 201810515538 A CN201810515538 A CN 201810515538A CN 108504136 B CN108504136 B CN 108504136B
Authority
CN
China
Prior art keywords
anthraquinone
disperse dyes
reactive disperse
dyeing
blue
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810515538.4A
Other languages
Chinese (zh)
Other versions
CN108504136A (en
Inventor
龙家杰
樊月
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201810515538.4A priority Critical patent/CN108504136B/en
Publication of CN108504136A publication Critical patent/CN108504136A/en
Application granted granted Critical
Publication of CN108504136B publication Critical patent/CN108504136B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/06—Anthracene dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/465—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an acryloyl group, a quaternised or non-quaternised aminoalkyl carbonyl group or a (—N)n—CO—A—O—X or (—N)n—CO—A—Hal group, wherein A is an alkylene or alkylidene group, X is hydrogen or an acyl radical of an organic or inorganic acid, Hal is a halogen atom, and n is 0 or 1
    • C09B62/467—Anthracene dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • D06P3/148—Wool using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

The invention discloses a kind of blue anthraquinone reactive disperse dyes and preparation method thereof, dyestuff is suitable for supercritical CO2Fluid dyeing technology.Its precursor structure of reactive disperse dyes provided by the invention is anthraquinone ring, and also with the amino that can be reacted with active group, active group includes the group that dichloro s-triazine, a chloro-s-triazine, α-bromopropene amide, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) etc. can react with fiber, overcomes that current anthraquinone reactive disperse dyes structure is single, deficiencies of less varieties.Anthraquinone reactive disperse dyes provided by the invention can be used for supercritical CO2The fibers such as cotton, wool, silk are especially had good dyeing effect by the dyeing of natural fiber and its dyeing process of blended fabric in fluid dyeing.Every fastness index of fabric is preferable after dyeing.The synthesis technology of dyestuff is simple, and reaction condition is mild, and manufacturing cost is low, and application is strong.

Description

A kind of blue anthraquinone reactive disperse dyes and preparation method thereof
Technical field
The present invention relates to one kind to be used for supercritical CO2Anthraquinone reactive disperse dyes of dyeing and preparation method thereof belongs to dye Expect synthesis technical field.
Background technique
Supercritical CO2Staining technique is with supercritical CO2Fluid is the dyeing and finishing that dyeing medium carries out dyeing process to textile New technology starts from the 1980s, its main feature is that addition auxiliary agent is not required to, also without waste water generation.Textile is in supercritical CO2Stream Staining technique in body enters the scale study in pilot scale stage in laboratory, is expected to substituting traditional water-bath technique in the future. It alleviates the demand to water significantly, while also greatly reducing the discharge amount of sewage, fundamentally solves dyeing Pollution problem to environment.In supercritical CO2Dyeing product good level-dyeing property obtained in body can reach the same of traditional water bath dyeing And other effects, and after the completion of dyeing, residual dye is in powdered, dyestuff and CO2Gas recoverable, and product dyed thereby is in drying State, without drying and processing etc..Compared with traditional water bath decoration method, energy can be saved and reach 20% or more, dyeing kinetics compare water-bath 3~6 times are improved, process time can shorten 1~2h.
The supercritical dyeing technology relative maturity of the synthetic fibers such as terylene, and the dyeing of natural fiber is asked there is also many Topic, applicable dye species are few.Reactive disperse dyes can preferably solve natural fiber super due to the special nature of itself Critical CO2It is difficult to the problem of dyeing in fluid, and gradually develops towards blended fabric supercritical non-aqueous dyeing application direction.It is super Critical CO2Non-aqueous dyeing develops dedicated dye, is particularly applied to the dyestuff of the natural fibers such as cotton, silk, wool, increases dyestuff Kind expands the scope of application, is current urgent problem to be solved.In terms of reactive disperse dyes synthesis, in the prior art about The report of anthraquinone ring is less, and method is also relatively simple.Usually activity is introduced directly on the basis of existing disperse dyes Base, it is of less types.Therefore, how to make the structural diversification of reactive disperse dyes, solve that reactive disperse dyes type is few, application The deficiencies of not strong, it has also become the key of breakthrough bottleneck.
Summary of the invention
The present invention is in view of the deficienciess of the prior art, provide a kind of suitable for supercritical CO2The anthraquinone knot of fluid dyeing Reactive disperse dyes of structure and preparation method thereof, can solve that current anthraquinone reactive disperse dyes structure is single, less varieties, Wu Faman Deficiency present in the dyeing of sufficient natural fiber；Reactive disperse dyes is applied to supercritical CO2Non-aqueous dyeing or traditional dyeing and finishing Processing has a good dyeability to the natural fibers such as cotton, hair, silk and its blended textile, dyestuff spread into fiber with The speed of upper dye is fast, and dyeing quality is good, and manufacturing cost is low.
Realize that the technical solution of the object of the invention is to provide a kind of blue anthraquinone reactive disperse dyes, structural formula is as follows:
,
In formula, n >=2；R is reactive active group.
Preferred embodiment of the invention is: n 2,4 or 6；Reactive active group R includes dichloro s-triazine, a chlorine equal three Piperazine, α-bromopropene amide, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) and its derivative.
Technical solution of the present invention further includes the preparation method of blue anthraquinone reactive disperse dyes as described above, including as follows Step:
(1) by 1,4- dihydroxy anthraquinone, 1,4- diamino-anthraquinone leuco compound, 1:1.5~1:3 is added to reaction in molar ratio In container, then the diamines of aniline, carbon chain lengths n >=2 is dissolved in and is added to after isobutanol solution in the reaction vessel, obtained To reaction solution, the molar ratio of Isosorbide-5-Nitrae-dihydroxy anthraquinone and aniline is 1:2~1:7.5；
(2) under conditions of nitrogen protection, temperature are 55~90 DEG C, after being stirred to react liquid reaction 2h, 108 DEG C are warming up to, After being stirred to react 3h, 95 DEG C are cooled to, copper acetate and piperidine catalyst is added, then be warming up to 108 DEG C；1,4- dihydroxy anthraquinone with The molar ratio of copper acetate is 1:1.5~1:6；
(3) under conditions of temperature is 108 DEG C, oxygen, 2~5h of oxidation reaction are passed through；It is pure through separating after being cooled to room temperature Change processing obtains a kind of blue solid, is as used for the presoma of anthraquinone reactive disperse dyes；
(4) presoma prepared by step (3) is reacted with reactivity active group R, it is living obtains a kind of blue anthraquinone Property disperse dyes.
The preferred embodiment of above-mentioned preparation method is: the reactive active group R includes dichloro s-triazine, a chlorine equal three Piperazine, α-bromopropene amide, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) and its derivative；The carbon chain lengths n of the diamines is 2,4 or 6.
Compared with prior art, the beneficial effects of the present invention are the blue anthraquinone reactive disperse dyes structure letters of: offer Single, the amino reactivity contained in precursor structure is strong, can be used for supercritical CO2The dyeing of natural fiber in fluid dyeing. Using blue anthraquinone reactive disperse dyes provided by the invention, there is good dyeability to natural fibers such as cotton, silk, wools Can, dyeing quality is good, and the colour fading series of fastness to soaping reaches 3~4 grades, and few to the staining of other fabrics, staining series reaches 4 ~5 grades, resistance to dry fastness reaches 3~4 grades, and wet rubbing fastness reaches 4~5 grades.Meanwhile blue anthraquinone provided by the invention Reactive disperse dyes reaction process is easily operated, and technique is easily controllable, and manufacturing cost is low, therefore, has a good application prospect.
Detailed description of the invention
Fig. 1 is that the ultraviolet-visible for measuring the presoma that the embodiment of the present invention 1 provides with U3010 ultraviolet specrophotometer is inhaled Receive spectrum.
Fig. 2 is the infrared spectroscopy tested using the presoma that FTIR spectrum provides the embodiment of the present invention 1 Figure.
Fig. 3 is to measure the blue anthraquinone reactive disperse dyes that the embodiment of the present invention 1 provides with U3010 ultraviolet specrophotometer Uv-visible absorption spectra.
Fig. 4 is to be carried out using FTIR spectrum to the blue anthraquinone reactive disperse dyes that the embodiment of the present invention 1 provides The infrared spectrogram of test.
Specific embodiment
With reference to the accompanying drawings and examples, further to technical solution of the present invention to be specifically described.
Embodiment 1:
The present embodiment is reacted by preparing the presoma of blue anthraquinone reactive disperse dyes with for the reacting of ethylenediamine Formula are as follows:
。
Specific steps are as follows:
1,4- dihydroxy anthraquinone 0.24g and its leuco compound 1,4- diamino-anthraquinone 0.619g and 0.462ml isobutanol is taken to set It is dissolved in the isobutanol solution of 15ml20% in there-necked flask, while by 6.840mL aniline and 1ml ethylenediamine, is protected in 60 DEG C of nitrogen Insulated and stirred 2h under the conditions of shield；108 DEG C of boiling stirring 3h at this temperature are warming up to after heat preservation 2h；It is cooled to 95 DEG C of addition acetic acid The molar ratio of copper and piperidine catalyst, Isosorbide-5-Nitrae-dihydroxy anthraquinone and copper acetate is 1:1.5, and appropriate piperidines is warming up to 108 DEG C of boilings 3h；It is filled with dioxygen oxidation 3h；It is cooled to room temperature, reaction is completed.It is eluant, eluent progress with petroleum ether and methylene chloride (1:3, v/v) Column separating purification is chromatographed, obtains blue solid, product is blue anthraquinone reactive disperse dyes presoma, the structural formula of product Are as follows:
。
It is 3 × 10 in precursor concentration using methylene chloride as solvent referring to Fig. 1-5Under conditions of mol/L, U3010 is used Type ultraviolet specrophotometer measures the uv-visible absorption spectra of presoma.As seen from Figure 1, using methylene chloride conduct When solvent, the characteristic absorption peak of blue anthraquinone reactive disperse dyes presoma is within the scope of 550~650nm, maximum absorption wave A length of 610nm, the presoma are blue.Fig. 1 the result shows that, it is provided in this embodiment be used for blue anthraquinone reactive disperse dyes The absorption band of presoma is wider, and the color of presoma is than darker.
Referring to attached drawing 2, examination of infrared spectrum is carried out to presoma provided in this embodiment using FTIR spectrum, In the infrared spectrogram of result figure 2,3460.34cm-1And 1567.09cm-1Place is respectively the stretching vibration of amino and imino group Peak；2924.19cm-1Place is the stretching vibration peak of methylene, 1644.58cm-1Carbonylic stretching vibration peak in the anthraquinone ring that place is.
Presoma provided in this embodiment is used to prepare the anthraquinone reactive disperse dyes using dichloro s-triazine as active group, Its reaction equation are as follows:
。
Specific step is as follows:
1.5mmol(0.277g) Cyanuric Chloride is dissolved in 5ml Isosorbide-5-Nitrae-dioxane, and places it in low-temp reaction In bath, temperature is controlled within the scope of 0~5 DEG C.Taking 1mmol(0.357g) dye precursor provided in this embodiment is dissolved in 15mL In Isosorbide-5-Nitrae-dioxane, 1mmol(0.106g) Na2CO3It is dissolved in 15mL water, the two is added dropwise in reaction system simultaneously, stirs 3h. After reaction, add water (about 350mL) to dilute, flocculent deposit is precipitated, filter, wash, vacuum drying obtains blue solid.Again It is that eluant, eluent carries out chromatography column separating purification with petroleum ether and methylene chloride (1:1, v/v), blue solid is obtained, as with dichloro S-triazine is the blue anthraquinone reactive disperse dyes of active group, separation yield 63%, structural formula are as follows:
。
Referring to attached drawing 3, using methylene chloride as solvent, dichloro s-triazine anthraquinone reactive disperse dyes manufactured in the present embodiment Concentration is 3.12 × 10-5Under conditions of mol/L, the ultraviolet-visible spectrum of obtained anthraquinone reactive disperse dyes is tested. The ultraviolet-ray visible absorbing of blue anthraquinone reactive disperse dyes provided in this embodiment is measured with U3010 type ultraviolet specrophotometer Spectrum.When Fig. 3 is shown using methylene chloride as solvent, the characteristic absorption peak of anthraquinone reactive disperse dyes is in 550~ Within the scope of 650nm, a length of 570nm of maximum absorption wave, for blue.By Fig. 3 it can also be seen that anthraquinone reactive disperse dyes absorption band It is wider, it is known that the active dispersal color is than darker.
Infrared spectroscopy survey is carried out to blue anthraquinone reactive disperse dyes provided in this embodiment using FTIR spectrum Examination, as a result referring to attached drawing 4.Fig. 4 shows the infrared spectrogram for showing reactive disperse dyes.Active dispersal indigo plant is in 2922cm-1Place For the unimodal of-NH-, show-the NH in presoma2It is substituted, obtains secondary amino group；In 1628cm-1There are the stretching vibrations of C=O at place Peak, and in 1557cm-1There are the stretching vibration peak of C=N, peak shape is sharp at place, this is as caused by the vibration of triazine ring skeleton；? 733-1There are the stretching vibration peaks of C-Cl at place.Thus it proves, the present invention is successfully prepared the dyestuff of shown structure.
Embodiment 2
The presoma that the embodiment of the present invention 1 provides is used to prepare using α-bromopropene amide as the anthraquinone activity of active group point Dissipate dyestuff, reaction equation are as follows:
。
Specific step is as follows:
Take 1mmol(0.357g) embodiment 1 provide dye precursor be dissolved in 15mL methylene chloride, temperature control 0 Within the scope of~5 DEG C.0.0015mol2 is taken, bis- bromo propionyl chloro of 3- is diluted in 5mL methylene chloride, and be slowly added dropwise, is warming up to 35 DEG C, 1h is stirred, 1mL triethylamine is added, stirs 3h.After reaction, add water (about 350mL) to dilute, flocculent deposit is precipitated, take out Filter is washed, and vacuum drying obtains blue solid.It is again that eluant, eluent carries out chromatographic column with petroleum ether and methylene chloride (1:2, v/v) It isolates and purifies, blue solid is obtained, as using α-bromopropene amide as the anthraquinone reactive disperse dyes of active group, structural formula Are as follows:
。
Due to amino strong containing reactivity in precursor construction provided in this embodiment, presoma can also with it is other anti- Answering property active group R reaction, obtains the blue anthraquinone reactive disperse dyes of different structure:,
Wherein, R can also be a chloro-s-triazine, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) and its derivative isoreactivity group.
Embodiment 3:
The present embodiment prepares blue anthraquinone reactive disperse dyes presoma, specific steps using Putriscine as reactant It is as follows:
1,4- dihydroxy anthraquinone 0.24g and its leuco compound 1,4- diamino-anthraquinone 0.619g and 0.462ml isobutanol is taken to set It is dissolved in the isobutanol solution of 15ml20% in there-necked flask, while by 6.840mL aniline and 1.5 ml Putriscines, 60 Insulated and stirred 2h under the conditions of DEG C nitrogen protection；108 DEG C of boiling stirring 3h at this temperature are warming up to after heat preservation 2h；It is cooled to 95 DEG C The molar ratio of addition copper acetate and piperidine catalyst, Isosorbide-5-Nitrae-dihydroxy anthraquinone and copper acetate is 1:3, and appropriate piperidines is warming up to 108 DEG C boiling 3h；It is filled with dioxygen oxidation 3h；It is cooled to room temperature, reaction is completed.It is elution with petroleum ether and methylene chloride (1:3, v/v) Agent carries out chromatography column separating purification, obtains blue solid, as blue anthraquinone reactive disperse dyes presoma, structural formula are as follows:
。
Due to amino strong containing reactivity in precursor construction provided in this embodiment, referring to the side of embodiment 1 or 2 Method, presoma can be anti-with dichloro s-triazine, a chloro-s-triazine, α-bromopropene amide, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) and its derivative isoreactivity group It answers, obtains the blue anthraquinone reactive disperse dyes of different structure.
Embodiment 4:
The present embodiment is to prepare blue anthraquinone reactive disperse dyes presoma, specifically with for the reaction of 1,6- hexamethylene diamine Steps are as follows: 1,4- dihydroxy anthraquinone 0.24g and its leuco compound 1,4- diamino-anthraquinone 0.619g and 0.462ml isobutanol being taken to set In there-necked flask, while by 6.840mL aniline and 3.3 ml 1,6- hexamethylene diamine is dissolved in the isobutanol solution of 15ml20%, 60 Insulated and stirred 2h under the conditions of DEG C nitrogen protection；108 DEG C of boiling stirring 3h at this temperature are warming up to after heat preservation 2h；It is cooled to 95 DEG C The molar ratio of addition copper acetate and piperidine catalyst, Isosorbide-5-Nitrae-dihydroxy anthraquinone and copper acetate is 1:5, and appropriate piperidines is warming up to 108 DEG C boiling 3h；It is filled with dioxygen oxidation 3h；It is cooled to room temperature, reaction is completed.It is elution with petroleum ether and methylene chloride (1:3, v/v) Agent carries out chromatography column separating purification, obtains blue solid, as blue anthraquinone reactive disperse dyes presoma, structural formula are as follows:
。
Due to amino strong containing reactivity in precursor construction provided in this embodiment, referring to the side of embodiment 1 or 2 Method, presoma can be anti-with dichloro s-triazine, a chloro-s-triazine, α-bromopropene amide, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) and its derivative isoreactivity group It answers, obtains the blue anthraquinone reactive disperse dyes of different structure.
Embodiment 5:
Use the embodiment of the present invention 1 provide using dichloro s-triazine as active group when, blue anthraquinone reactive disperse dyes use In supercritical CO2Dyeing processing is carried out to cotton, wool and silk in fluid.
Knitting cotton, wool and each 1g of silk fabric are taken, supercritical CO is respectively placed in2In fluid dyeing caldron, active dispersal The dosage of dyestuff is 2%omf, and suitable catalyst is added.40min, heating rate are kept the temperature under conditions of 25MPa, 130 DEG C For 2 DEG C/min.Fabric is taken out after dyeing to detect for dyeability.The result shows that anthraquinone activity provided in this embodiment Disperse dyes have good dyeability to natural fibers such as cotton, silk, wools, and dyeing quality is good.It dyes on the fabric Afterwards, every dye fastness index is good, wherein fastness to soaping is good, and colour fading series can reach 3~4 grades；Other fabrics are stained with Pornographic condition is less, and staining series can reach 4~5 grades；Resistance to dry fastness can reach 3~4 grades, and wet rubbing fastness can reach 4~5 grades.
By supercritical CO provided in this embodiment2Fluid dyeing technology, the difference provided using other embodiments of the present invention The blue anthraquinone reactive disperse dyes of structure is used to carry out dyeing processing to cotton, wool and silk, the dyeability of fabric and Effect is identical as the present embodiment measured result.
Blue anthraquinone reactive disperse dyes provided by the invention, structure is simple, and reaction process is easily operated, precursor structure In the amino reactivity that contains it is strong, can be used for supercritical CO2The dyeing of natural fiber in fluid dyeing.It is provided using the present invention Blue anthraquinone reactive disperse dyes, to the natural fibers such as cotton, silk, wool have good dyeability, dyeing quality is good, Manufacturing cost is low, therefore, has a good application prospect.

Claims (2)

1. a kind of blue anthraquinone reactive disperse dyes, it is characterised in that structural formula is as follows:
,
In formula, n 2,4 or 6；R is reactive active group, is selected from dichloro s-triazine, a chloro-s-triazine or α-bromopropene amide.
2. a kind of preparation method of blue anthraquinone reactive disperse dyes as described in claim 1, it is characterised in that including as follows Step:
(1) by 1,4- dihydroxy anthraquinone, 1,4- diamino-anthraquinone leuco compound, 1:1.5~1:3 is added to reaction vessel in molar ratio In, then aniline, the diamines that carbon chain lengths n is 2,4 or 6 be dissolved in and be added in the reaction vessel after isobutanol solution, Obtain reaction solution, the molar ratio of Isosorbide-5-Nitrae-dihydroxy anthraquinone and aniline is 1:2~1:7.5；
(2) under conditions of nitrogen protection, temperature are 55~90 DEG C, after being stirred to react liquid reaction 2h, 108 DEG C are warming up to, stirring After reacting 3h, 95 DEG C are cooled to, copper acetate and piperidine catalyst is added, then be warming up to 108 DEG C；1,4- dihydroxy anthraquinone and acetic acid The molar ratio of copper is 1:1.5~1:6；
(3) under conditions of temperature is 108 DEG C, oxygen, 2~5h of oxidation reaction are passed through；After being cooled to room temperature, place is isolated and purified Reason obtains a kind of blue solid, is as used for the presoma of anthraquinone reactive disperse dyes；
(4) presoma prepared by step (3) is reacted with reactivity active group R, obtains a kind of blue anthraquinone activity point Dyestuff is dissipated, reactive active group R is selected from dichloro s-triazine, a chloro-s-triazine or α-bromopropene amide.
CN201810515538.4A 2018-05-25 2018-05-25 A kind of blue anthraquinone reactive disperse dyes and preparation method thereof Active CN108504136B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810515538.4A CN108504136B (en) 2018-05-25 2018-05-25 A kind of blue anthraquinone reactive disperse dyes and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810515538.4A CN108504136B (en) 2018-05-25 2018-05-25 A kind of blue anthraquinone reactive disperse dyes and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108504136A CN108504136A (en) 2018-09-07
CN108504136B true CN108504136B (en) 2019-09-06

Family

ID=63401619

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810515538.4A Active CN108504136B (en) 2018-05-25 2018-05-25 A kind of blue anthraquinone reactive disperse dyes and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108504136B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111424446A (en) * 2020-05-21 2020-07-17 浙江爱利斯染整有限公司 Supercritical dyeing method
CN111424444A (en) * 2020-05-21 2020-07-17 浙江爱利斯染整有限公司 Composition for supercritical dyeing and application thereof
CN111636222A (en) * 2020-06-08 2020-09-08 浙江越新印染有限公司 Fluid composition and use thereof for anhydrous dyeing with supercritical carbon dioxide
CN111635647A (en) * 2020-06-08 2020-09-08 浙江越新印染有限公司 Red dyeing composition and application thereof in supercritical carbon dioxide anhydrous dyeing
CN116411466A (en) * 2021-12-30 2023-07-11 江苏欣鑫纺织科技有限公司 Processing method of efficient multifunctional indoor decorative flannelette
CN115260785B (en) * 2022-08-09 2024-02-06 南通大学 Double (trisiloxane) -anthraquinone-containing disperse dye
CN116694101A (en) * 2023-06-12 2023-09-05 大连工业大学 Modified anthraquinone type reactive disperse dye and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5367039A (en) * 1988-07-06 1994-11-22 Nippon Paint Company, Ltd. Production of colored vinyl polymer particles by polymerizing a vinyl polymerizable monomer with a polymerizable dye
DE3915066A1 (en) * 1989-05-09 1990-11-15 Bayer Ag Stabilized polyorganosiloxanes and their use as power transfer media

Also Published As

Publication number Publication date
CN108504136A (en) 2018-09-07

Similar Documents

Publication Publication Date Title
CN108504136B (en) A kind of blue anthraquinone reactive disperse dyes and preparation method thereof
Xiao et al. Eco-friendly approaches for dyeing multiple type of fabrics with cationic reactive dyes
Zhang et al. Ecofriendly synthesis and application of special disperse reactive dyes in waterless coloration of wool with supercritical carbon dioxide
CN102720078B (en) Method for dyeing cotton-dacron-chinlon combined silk fabric
CN107057401B (en) Dichloro s-triazine type reactive disperse dyes based on anthraquinone and preparation method thereof
Zheng et al. Dyeing properties of novel electrolyte‐free reactive dyes on cotton fibre
Gao et al. Synthesis of reactive disperse dyes containing halogenated acetamide group for dyeing cotton fabric in supercritical carbon dioxide
CN112239604B (en) Reactive disperse dye, preparation method and dyeing application thereof
Yan et al. Development of a special SCFX-AnB3L dye and its application in ecological dyeing of silk with supercritical carbon dioxide
Xiao et al. One-bath union dyeing of wool/acrylic blend fabric with cationic reactive dyes based on azobenzene
CN109056392A (en) A kind of colouring method of natural dye
CN103080414A (en) Mixtures of fibre-reactive dyes and their use in a method for trichromatic dyeing or printing
CN104016880B (en) The presoma of special azo reactive disperse dyes and purposes
US5938793A (en) Process for increasing the sun protection factor of cellulosic fibre materials
CN108586274A (en) A kind of presoma and preparation method thereof of blue anthraquinone reactive disperse dyes
CN109054438A (en) Dedicated azo dyes of natural fiber non-aqueous dyeing and preparation method thereof in supercritical fluid CO 2
CN106752077B (en) A kind of blue active dye composition and its preparation method and application
WO2019223016A1 (en) Blue anthraquinone active disperse dye and preparation method therefor
Elgemeie et al. Microwave synthesis, photophysical properties of novel fluorescent iminocoumarins and their application in textile printing
Mousa et al. Dyeing of nylon 6 fabric with a new bifunctional vinyl sulphone reactive disperse dye
CN109206943A (en) High color fastness blue disperse dye mixture and preparation method thereof
CN106833015B (en) A kind of more chromophoric group dark brown reactive dye of trisazo- and its preparation method and application
CN109535095A (en) Aryl primary amine fluorescent whitening agent and preparation method thereof suitable for silk
Li et al. Synthesis and application of crosslinking blue anthraquinone polyamine dye with high fixation
WO2019223015A1 (en) Precursor of blue anthraquinone active disperse dye and preparation method therefor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant